CN113773682B - Hydrophobic material for low-temperature plasma chemical vapor deposition and method for preparing nano-film by using same - Google Patents
Hydrophobic material for low-temperature plasma chemical vapor deposition and method for preparing nano-film by using same Download PDFInfo
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Abstract
The invention discloses a hydrophobic material for low-temperature plasma chemical vapor deposition and a method for preparing a nano-film by using the same. The hydrophobic material includes: fluorine-containing acrylate monomer, polyol ether ester and polymerization inhibitor; wherein the mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is 5-10%; the mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm. The hydrophobic material for low-temperature plasma chemical vapor deposition has better fluidity even in a low-temperature environment, can avoid the solidification and self-polymerization of the hydrophobic material, can realize continuous production by using the hydrophobic material to carry out the low-temperature plasma chemical vapor deposition, improves the production efficiency, generates a crosslinking effect, and is beneficial to improving the quality of a nano film and improving the defense capability of the nano film.
Description
Technical Field
The invention relates to a hydrophobic material for low-temperature plasma chemical vapor deposition and a method for preparing a nano-film by using the same, belonging to the field of functional materials and preparation thereof.
Background
The preparation of nano hydrophobic films by using low-temperature plasma chemical vapor deposition is widely applied. The hydrophobic material that is currently more commonly used may be a fluoroacrylate monomer. However, such monomers have the disadvantages of poor low temperature stability and susceptibility to self-polymerization. In particular, the fluoroacrylate monomers tend to solidify at temperatures below 10 ℃, resulting in poor flow and possibly even complete crystallization. The fluorine-containing acrylate monomer has the characteristics that the fluorine-containing acrylate monomer is easy to cause the blockage of low-temperature plasma chemical vapor deposition equipment in the preparation process of the nano-film, so that the continuous production cannot be realized.
Disclosure of Invention
The invention provides a hydrophobic material for low-temperature plasma chemical vapor deposition and a method for preparing a nano film by using the hydrophobic material, aiming at the problem that the fluorine-containing acrylate monomer is easy to solidify or crystallize in the process of preparing the nano film by low-temperature plasma chemical vapor deposition so as to cause the blockage of low-temperature plasma chemical vapor deposition equipment. The hydrophobic material for low-temperature plasma chemical vapor deposition has better fluidity even in a low-temperature environment (such as 5-10 ℃), can avoid the solidification and self-polymerization of the hydrophobic material, can realize continuous production by using the hydrophobic material to carry out the low-temperature plasma chemical vapor deposition, improves the production efficiency, generates a crosslinking effect, and is beneficial to improving the quality of a nano film and enhancing the defense capability of the nano film. The defensive power refers to the barrier capability of the nano-film against the erosion of water, salt solution, acid and alkali and other liquids.
In a first aspect, the present invention provides a hydrophobic material for low temperature plasma chemical vapor deposition. The hydrophobic material includes: fluorine-containing acrylate monomer, polyol ether ester and polymerization inhibitor; wherein the mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is 5-10%; the mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm.
Preferably, the polyol ether ester comprises at least one of propylene glycol (mono) methyl ether propionate, polyether polyol acetate, fatty alcohol polyether sulfonate, dodecanol ether phosphate, propylene glycol monomethyl ether propionate, isomeric tridecanol ether phosphate, and fatty alcohol ether phosphate.
Preferably, the polymerization inhibitor is at least one of a chain transfer type polymerization inhibitor and a radical type polymerization inhibitor.
Preferably, the polymerization inhibitor is benzoquinone, phenothiazine and piperidine nitrogen-oxygen free radical type polymerization inhibitor according to the mass ratio of 1-50%:1-50%:1-50% of composite polymerization inhibitor.
Preferably, the hydrophobic material further comprises an ethanol solution of a silane coupling agent, and the mass ratio of the fluorine-containing acrylate monomer to the ethanol solution of the silane coupling agent is 70:20-90:5.
preferably, the silane coupling agent is at least one of vinyl propyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethyl silane, 3-butenyl trimethyl silane, vinyl tributyl ketoximino silane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 3-glycidyl ether oxypropyl triethoxy silane, gamma-glycidyl ether oxypropyl trimethoxy silane, KH540, A171, KH570, KH550 and KH 560.
Preferably, the silane coupling agent is KH570, KH550 and KH560 according to a mass ratio of 1-50:1-50: 1-50.
In a second aspect, the present invention provides a method for preparing the hydrophobic material for low temperature plasma chemical vapor deposition as described in any one of the above. And (2) uniformly mixing the fluorine-containing acrylate monomer, the polyol ether ester and the polymerization inhibitor, or uniformly mixing the fluorine-containing acrylate monomer, the polyol ether ester, the polymerization inhibitor and an ethanol solution of a silane coupling agent to obtain the hydrophobic material for low-temperature plasma chemical vapor deposition.
In a third aspect, the invention provides a method for preparing a nano film from the hydrophobic material for low-temperature plasma chemical vapor deposition, which is described in any one of the above. The method comprises the following steps:
activation pretreatment: putting a workpiece to be processed into a reaction cavity, introducing pretreatment gas into the reaction cavity, starting a radio frequency power supply, and performing activation treatment on the surface of the workpiece in the reaction cavity by using plasma;
depositing a nano film: introducing the vaporized hydrophobic material into a reaction cavity, and depositing a nano film on the surface of the workpiece under pulse waves or continuous waves;
breaking vacuum: slowly breaking vacuum in the reaction cavity;
and (3) post-treatment: and sealing and packaging the workpiece on which the nano film is deposited, and carrying out temperature and humidity adjustment treatment.
Preferably, in the step of depositing the nano film, the film plating power is 100-1000W; the deposition time is 10-120min; the thickness of the nano film is 50-1000nm.
Preferably, in the step of the activation pretreatment, the pretreatment gas is argon, and the flow rate of the pretreatment gas is 10-1000sccm; the power of the radio frequency power supply is 100-1000W; the pressure of the reaction cavity is 0.01-0.1mbar; the activation time is below 60min.
Drawings
FIG. 1 is a static contact angle test chart of the nanomembrane of example 2;
fig. 2 is a static contact angle test graph of the nanomembrane of example 3.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage refers to a mass percentage.
The present disclosure provides a hydrophobic material for low temperature plasma chemical vapor deposition. The hydrophobic material includes: fluorine-containing acrylate monomer, polyol ether ester and polymerization inhibitor.
The fluorine-containing acrylate monomer is an acrylate monomer which has a fluorine-containing substituent in a straight chain and simultaneously contains C = O and C = C functional groups. The molecular structure of the fluorine-containing acrylate monomer contains olefin double bonds, and pi bonds in the double bonds are easy to be excited and broken in a plasma atmosphere to generate polymerization reaction, so that a film material with a certain crosslinking degree is formed, and the film quality is good. As an example, the fluorine-containing acrylate monomer includes, but is not limited to, at least one of 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorododecyl) ethyl acrylate, 2-perfluorooctyl ethyl acrylate, 1H, 2H-perfluorooctanol acrylate, 2- (perfluorobutyl) ethyl acrylate, (2H-perfluoropropyl) -2-acrylate, and (perfluorocyclohexyl) methacrylate.
According to a similar compatibility principle, the polyol ether ester and the fluorine-containing acrylate monomer have excellent compatibility, so that the polyol ether ester has good dissolving capacity for the fluorine-containing acrylate monomer. In addition, the polyol ether ester has an anti-freezing function, can reduce the melting point of the fluorine-containing acrylate monomer, and can be stably kept in a liquid state at the temperature of more than 5-10 ℃ so as to have good fluidity and processability. Preferably, the polyol ether ester comprises at least one of propylene glycol (mono) methyl ether propionate, polyether polyol acetate, fatty alcohol polyether sulfonate, dodecanol ether phosphate, propylene glycol monomethyl ether propionate, isomeric tridecanol ether phosphate, and fatty alcohol ether phosphate.
It is stated here that anti-freezing agents such as alcohol solvents and acetone are not suitable for use in the hydrophobic material of the present invention. The reason is that: the alcohol antifreeze belongs to a polar solvent, has poor compatibility with a fluorine-containing acrylate monomer, is easy to delaminate under a low-temperature condition, shows a state that the fluorine-containing acrylate monomer is solidified but the alcohol antifreeze keeps a liquid state, and is difficult to realize an ideal antifreeze effect. Acetone also belongs to polar solvents, has a low boiling point, is more volatile than alcohol antifreeze agents, and is not suitable for being used as the antifreeze agent of the hydrophobic material.
The mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is 5-10%. If the mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is less than 5%, the anti-freezing performance of the hydrophobic material is poor, and plasma vapor deposition of a hydrophobic film is difficult to continuously perform due to the solidification of the fluorine-containing acrylate monomer in a low-temperature environment. In tests, it was found that if the mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is higher than 10%, the hydrophobic property of the coating film is weakened, because the existence of a large number of ether linkages is not good for the hydrophobic property of the finally deposited nano film layer.
The fluoroacrylate monomers have a tendency to self-polymerize. In the process of preparing the nano film by using the fluorine-containing acrylate monomer to carry out low-temperature plasma chemical vapor deposition, the fluorine-containing acrylate monomer is easy to cause viscosity due to self-polymerization, the fluidity is reduced, and the plasma deposition cannot be carried out. By adding the polymerization inhibitor into the hydrophobic material, the self-polymerization of the fluorine-containing acrylate monomer can be slowed down or even avoided. The polymerization inhibitor may be one conventional in the art, including, but not limited to, at least one of a chain transfer type polymerization inhibitor and a radical type polymerization inhibitor. Preferably, the polymerization inhibitor is 1-50% of benzoquinone, phenothiazine and piperidine nitroxide free radical polymerization inhibitor by mass ratio: 1-50%:1-50% of composite polymerization inhibitor. The composite polymerization inhibitor prevents the self-polymerization of the fluorine-containing acrylate monomer to the maximum extent through the comprehensive polymerization inhibition of two modes, namely chain transfer and free radicals. The piperidine nitroxide free radical type polymerization inhibitor comprises at least one of 4-hydroxy-2,2,6,6 tetramethyl piperidine nitroxide radical polymerization inhibitor TMP, 1,1 diphenyl-2-picrylhydrazine DPPH, trityl free radical, nitroxide radical piperidinol and nitroxide radical piperidinone.
The mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm, preferably 80-200ppm. The mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is controlled within the above range, and the induction period can be controlled to optimize the polymerization inhibition effect.
Preferably, the hydrophobic material further comprises an ethanol solution of a silane coupling agent. The mass ratio of the fluorine-containing acrylate monomer to the ethanol solution of the silane coupling agent is 70:20-90:5. thus, the hydrophobic property of the monomer is not influenced while the crosslinking effect is considered. If the content of the silane coupling agent is too high, excessive crosslinking is easily caused, and the hydrophobic property of the monomer is also reduced due to the excessive content of the ethanol. The content of the silane coupling agent is too high, the hydrophobic material is easy to become sticky after being placed in a material liquid tank for a period of time, and the fluidity is obviously reduced. If the content of the silane coupling agent is too low, the crosslinking effect is not obvious, and the quality of the film layer is poor.
The mass percentage of the silane coupling agent in the ethanol solution of the silane coupling agent can be 1-20%. The silane coupling agent can promote the crosslinking of the fluorine-containing acrylate monomer in the film coating process, for example, the silicon-oxygen bond or the vinyl-containing silane double bond of the silane coupling agent can generate addition reaction with the olefin double bond of the fluorine-containing acrylate monomer, so that a nano film with good continuity can be formed, the compactness and the film coating quality of a film layer are improved, the bonding force between the nano film and a substrate is improved, and the protective and insulating capability of the film coating is improved.
The type of the silane coupling agent can be adjusted adaptively according to the crosslinking structure and the crosslinking effect. The silane coupling agent includes, but is not limited to, at least one of vinyl propyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethylsilane, 3-butenyl trimethylsilane, vinyl tributyrinoxime silane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 3-glycidyl ether oxypropyltriethoxysilane, gamma-glycidyl ether oxypropyltrimethoxysilane, KH540, A171, KH570, KH550, and KH 560. Preferably, the silane coupling agent is KH570, KH550 and KH560 according to a mass ratio of 1-50:1-50: 1-50. The composite silane coupling agent is beneficial to improvement of coating quality compared with a single silane coupling agent, because: the composite silane coupling agent has various reaction functional groups, so that the crosslinking reaction is easier to realize, different silane structures can be introduced, and the crosslinking effect is better. A single silane coupling agent reacts with the functional monomer to a relatively limited degree and may not crosslink completely or sufficiently.
The method for preparing the hydrophobic material for low temperature plasma chemical vapor deposition according to the present invention is described next. Theoretically, all the raw materials of the hydrophobic material are uniformly mixed.
Can be as follows: and (2) uniformly mixing the fluorine-containing acrylate monomer, the polyol ether ester and the polymerization inhibitor, or uniformly mixing the fluorine-containing acrylate monomer, the polyol ether ester, the polymerization inhibitor and an ethanol solution of a silane coupling agent to obtain the hydrophobic material for low-temperature plasma chemical vapor deposition.
The following steps are also possible: adding polyol ether ester into the fluorine-containing acrylate monomer, and stirring to obtain a first mixture. Adding a polymerization inhibitor into the first mixture, and continuing to perform second stirring to obtain a second mixture. And adding an ethanol solution of a silane coupling agent into the second mixture, and stirring to obtain the hydrophobic material for low-temperature plasma chemical vapor deposition. The stirring time of the above stirring may be independently selected from 1 to 60min.
The method for preparing the nano-film by using the hydrophobic material for low-temperature plasma chemical vapor deposition is also shown below. The method for depositing the hydrophobic film is a conventional method in the field and is not the innovation point of the invention. It should be understood that the adjustment of the corresponding parameters can be performed by those skilled in the art according to the actual situation.
And (4) activation pretreatment. It may also be referred to as a plasma activation pretreatment. And putting a workpiece to be treated into the reaction cavity, introducing pretreatment gas into the reaction cavity, starting a radio frequency power supply, and performing activation treatment on the surface of the workpiece in the reaction cavity by using plasma. The pretreatment gas may be argon. The surface of the workpiece is subjected to plasma surface activation through argon, so that the surface of the workpiece can be cleaned, and the reaction potential energy is reduced. In some embodiments, the flow rate of the pretreatment gas is 10 to 1000sccm; the power of the radio frequency power supply is 100-1000W; the pressure of the reaction cavity is 0.01-0.1mbar; the activation time is below 60min. Thus, the deposition of the hydrophobic material is facilitated, and the binding force of the film layer is improved.
Vaporization of the hydrophobic material. The hydrophobic material may be vaporized in a heated cup. The heating temperature of the heating cup is, for example, 75 to 100 ℃.
Depositing a nano film: and introducing the vaporized hydrophobic material into a reaction cavity, adjusting the pressure of the reaction cavity, and depositing a nano film on the surface of the workpiece under pulse waves or continuous waves. The pressure in the reaction chamber may be in the range of 0.01 to 0.2mbar, for example 0.06mbar. The power of the pulse wave is 100-1000W. The power of the continuous wave is 10-1000W. The vaporized hydrophobic material is dripped at a frequency of 1S/droplet to 20S/droplet (preferably 5S/droplet to 20S/droplet, more preferably 12S/droplet to 20S/droplet) in the flow rate. The deposition time of the hydrophobic film is 10-120min. The thickness of the nano film is 50-1000nm.
When the nano film is deposited, argon gas is also introduced as carrier gas while the vaporized hydrophobic material (monomer vapor) is introduced. The flow rate of the carrier gas can be 50-500sccm, such as 100sccm. When the hydrophobic material is deposited, the interference of oxidizing atmosphere can be prevented by adopting the assistance of inert gas argon, and the deposition of the hydrophobic nano film is realized under the higher vacuum condition.
Breaking vacuum: the reaction chamber was slowly evacuated. Breaking vacuum means that the pressure of a closed space with a certain vacuum degree is recovered until the pressure is the same as the external pressure. The temperature and pressure at the time of depositing the nano-film are constantly maintained for 20min or less, for example, 5min, and then the slow vacuum breaking process is completed within 10 min. Breaking the vacuum facilitates deposition and attachment of the hydrophobic material. The vacuum breaking time is related to the coating vacuum degree and the coating time. The larger the vacuum degree of the coating film is, the longer the vacuum breaking time is; the longer the coating time, the longer the vacuum breaking time.
And (3) post-treatment: and sealing and packaging the workpiece on which the nano film is deposited, and carrying out temperature and humidity adjustment treatment. And (3) hermetically packaging the workpiece on which the nano film is deposited, and placing the workpiece in a constant temperature and humidity environment for 20-45min. The temperature of the environment is 25-60 ℃, preferably 45 ℃; the humidity is 1-15%, preferably 5%. The post-treatment can ensure that the sample can isolate oxygen and moisture in the air, avoid the film layer to be polluted and further stabilize the film layer.
The nano film prepared by the method has a static contact angle of 130-160 degrees, preferably 140-155 degrees. The nano film has excellent hydrophobic effect.
In conclusion, the hydrophobic material for low-temperature plasma chemical vapor deposition has better fluidity in a low-temperature environment, can avoid the coagulation and self-polymerization of the hydrophobic material, can realize continuous production by using the hydrophobic material for low-temperature plasma chemical vapor deposition, improves the production efficiency, generates a crosslinking effect, and is beneficial to improving the quality of a nano film and improving the defense capability of the nano film.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Adding propylene glycol monomethyl ether propionate solvent into the fluorine-containing acrylate monomer, and stirring for 30min to be uniform to obtain a monomer mixed solution. The temperature of the monomer mixture was adjusted with an ice-water mixture, or the monomer mixture was placed in a refrigerator, and then the state of the monomer mixture was observed. The temperature of the monomer mixture was adjusted with ice water flexibly, but it was difficult to observe the stability for a long time. The monomer mixed liquid can be in a relatively closed and stable state in the refrigerator, and the stability of the monomer mixed liquid can be observed for a long time. Specific results are shown in table 1. The mass ratio in table 1 is the ratio of propylene glycol monomethyl ether propionate to the fluoroacrylate monomer.
TABLE 1 Low temperature stability of monomer mixtures of different mass ratios
It can be seen from table 1 that after propylene glycol methyl ether propionate with different mass ratios is added to the hydrophobic fluorine-containing acrylate monomer, the low-temperature stability limit temperatures of the obtained monomer mixture are respectively: 5 deg.C (10% added), 3 deg.C (20% added), and 2 deg.C (30% added). I.e. with corresponding low temperature extremes at different addition rates. Below this low temperature limit, the fluoroacrylate monomer begins to solidify. The propylene glycol methyl ether propionate solvent has good compatibility with the fluorine-containing acrylate monomer and good fluidity. Even if the monomer mixed solution is solidified at low temperature, once the monomer mixed solution is separated from the low temperature, the monomer mixed solution can still automatically and rapidly recover to liquid fluidity at normal temperature, and layering cannot occur.
For comparison, ethanol is added into the fluorine-containing acrylate monomer as a solvent, and the mixture is stirred for 30min to be uniform, so that a monomer mixed solution is obtained. The temperature of the monomer mixture was adjusted with an ice-water mixture, or the monomer mixture was placed in a refrigerator, and then the state of the monomer mixture was observed. Specific results are shown in table 2. The mass ratio in table 2 is the ratio of ethanol to the fluoroacrylate monomer.
TABLE 2 Low temperature stability of monomer mixtures of different mass ratios
The stability test finds that the monomer mixed solution of the propylene glycol methyl ether propionate solvent and the fluorine-containing acrylate monomer does not generate layering even if the monomer mixed solution is solidified at low temperature; but the monomer mixed solution of the absolute ethyl alcohol and the fluorine-containing acrylate monomer can be solidified at low temperature and delaminated obviously. After the monomer mixed solution of the propylene glycol methyl ether propionate solvent and the fluorine-containing acrylate monomer is solidified at low temperature, the liquid fluidity can be automatically and rapidly restored and the liquid is not layered when the monomer mixed solution is separated from the low-temperature ice water environment such as normal temperature. After the monomer mixed solution of the absolute ethyl alcohol and the fluorine-containing acrylate monomer is solidified at low temperature, the liquid state fluidity is slowly recovered after the monomer mixed solution is separated from the low-temperature ice water environment, such as normal temperature. This indicates that the propylene glycol methyl ether propionate solvent has good compatibility with the fluorine-containing acrylate monomer, and is superior to the compatibility of absolute ethyl alcohol and the fluorine-containing acrylate monomer.
In the following test, the test conditions were selected such that the mass ratio of propylene glycol monomethyl ether propionate to the fluorine-containing acrylate monomer was 10%, unless otherwise specified. At this time, the monomer mixture of the fluorine-containing acrylate monomer and the propylene glycol monomethyl ether propionate solvent can maintain good fluidity at 5 ℃, and does not delaminate and solidify. Adding a polymerization inhibitor into the monomer mixed solution, wherein the addition amount of the polymerization inhibitor is 100ppm, and after uniformly stirring, putting the mixture into a material liquid tank at normal temperature. After the mixture was left in the pot for 2 weeks, the dropping port of the pot was observed for the presence of crystals.
When MEHQ (p-hydroxyanisole) is used as a polymerization inhibitor, crystals are formed at the drip outlet. Thus, the MEHQ polymerization inhibitor cannot play a long-term stable polymerization inhibition effect on the fluorine-containing acrylate monomer. When the composite polymerization inhibitor consisting of benzoquinone BQ-phenothiazine PZ-piperidine nitroxide free radical type polymerization inhibitor (30% of benzoquinone BQ, 30% of phenothiazine PZ and the balance of piperidine nitroxide free radical type polymerization inhibitor) is used, the mixture keeps good fluidity after running in the plasma deposition equipment for the same time. The composite polymerization inhibitor having the above composition is known to exhibit an excellent polymerization inhibiting effect on the fluorine-containing acrylate monomer.
Example 2
The method for preparing a nano-film using a hydrophobic material for low temperature plasma chemical vapor deposition includes the steps of:
(1) Preparing a hydrophobic material from a fluorine-containing acrylate monomer, propylene glycol methyl ether propionate and a polymerization inhibitor; the polymerization inhibitor is benzoquinone, phenothiazine and piperidine nitrogen-oxygen free radical polymerization inhibitor, and the mass ratio is 30%:30%:40% of composite polymerization inhibitor; the propylene glycol methyl ether propionate accounts for 5-10% of the mass ratio of the fluorine-containing acrylate monomer; the mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm;
(2) Putting a workpiece to be processed into a reaction cavity, introducing pretreatment gas into the reaction cavity, starting a radio frequency power supply, and performing activation treatment on the surface of the workpiece in the reaction cavity by using plasma; the pretreatment gas is argon, the pressure of the reaction cavity is 0.08mbar, the flow of the argon is 100sccm, and the power of the continuous wave is 220W;
(3) Introducing the vaporized hydrophobic material into a reaction cavity, and depositing a nano film on the surface of the workpiece under pulse waves or continuous waves; dropping the vaporized hydrophobic material at the frequency of 12S/drop by controlling the flow, wherein the pressure of the reaction cavity is 0.06mbar, and the power of the pulse wave is 230W or the power of the continuous wave is 90W; the deposition time is 30min; introducing argon gas as a carrier gas while introducing the vaporized hydrophobic material, wherein the flow of the carrier gas is 100sccm;
(4) After the nano film deposition is finished, slowly breaking vacuum to the reaction cavity; the temperature and pressure of the deposited nano film are constantly maintained for 5min, and then the slow vacuum breaking is completed within 10 min;
(5) And after the vacuum breaking is finished, hermetically packaging the workpiece on which the nano film is deposited, and carrying out temperature and humidity adjustment treatment.
And (3) carrying out hydrophobic performance test on the nano-film according to GB/T30447-2013 contact angle measurement method of the nano-film or DB 44/T1232-2013 contact angle method of test method for measuring surface tension of solid coating, base material and pigment. Two samples were taken and the static contact angles of the nanomembrane were measured to be 150.2 ° and 149.5 °, respectively.
The water resistance rating test was performed according to IEC529 standard to demonstrate barrier performance. After the sample is placed in the water immersion tank, the distance from the bottom of the sample to the water surface is at least 1m, the distance from the top of the sample to the water surface is at least 0.15m, and the test time is 30min. Through tests, the waterproof grade of the test sample is IPX7 grade.
Example 3
The method for preparing a nano-film using a hydrophobic material for low temperature plasma chemical vapor deposition includes the steps of:
(1) Preparing a hydrophobic material from an ethanol solution of a fluorine-containing acrylate monomer, propylene glycol methyl ether propionate, a polymerization inhibitor and a silane coupling agent; the polymerization inhibitor is benzoquinone, phenothiazine and piperidine nitrogen-oxygen free radical polymerization inhibitor, and the mass ratio is 30%:30%:40% of composite polymerization inhibitor; the silane coupling agent is selected from KH570, KH550 and KH560 according to the mass ratio of 1-50:1-50: 1-50; the propylene glycol methyl ether propionate accounts for 5-10% of the mass ratio of the fluorine-containing acrylate monomer; the mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm; the mass ratio of the fluorine-containing acrylate monomer to the ethanol solution of the silane coupling agent is 70:20-90:5;
(2) Putting a workpiece to be processed into a reaction cavity, introducing pretreatment gas into the reaction cavity, starting a radio frequency power supply, and performing activation treatment on the surface of the workpiece in the reaction cavity by using plasma; the pretreatment gas is argon, the pressure of the reaction cavity is 0.08mbar, the flow of the argon is 100sccm, and the power of the continuous wave is 220W;
(3) Introducing the vaporized hydrophobic material into a reaction cavity, and depositing a nano film on the surface of the workpiece under pulse waves or continuous waves; dropping the vaporized hydrophobic material at the frequency of 12S/drop by controlling the flow, wherein the pressure of the reaction cavity is 0.06mbar, and the power of the pulse wave is 230W or the power of the continuous wave is 90W; the deposition time is 30min; introducing argon gas as a carrier gas while introducing the vaporized hydrophobic material, wherein the flow of the carrier gas is 100sccm;
(4) After the deposition of the nano film is finished, slowly breaking vacuum in the reaction cavity; the temperature and pressure of the deposited nano film are constantly maintained for 5min, and then the slow vacuum breaking is completed within 10 min;
(5) And after the vacuum breaking is finished, hermetically packaging the workpiece on which the nano film is deposited, and carrying out temperature and humidity adjustment treatment.
And (3) carrying out hydrophobic performance test on the nano-film according to GB/T30447-2013 'nano-film contact angle measuring method' or DB 44/T1232-2013 'test method contact angle method for measuring surface tension of solid coating, base material and pigment'. Two samples were taken and the static contact angles of the nanomembrane were measured to be 154.1 ° and 146.8 °, respectively.
The water resistance rating test was performed according to IEC529 standard to demonstrate barrier performance. After the sample is placed in the water immersion tank, the distance from the bottom of the sample to the water surface is at least 1m, the distance from the top of the sample to the water surface is at least 0.15m, and the test time is 30min. Through tests, the waterproof grade of the test sample is IPX7 grade.
Example 4
As in example 2, the only difference is: the mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is 20%.
And (3) carrying out hydrophobic performance test on the nano-film according to GB/T30447-2013 contact angle measurement method of the nano-film or DB 44/T1232-2013 contact angle method of test method for measuring surface tension of solid coating, base material and pigment. The nano-film of the present example has a static contact angle of about 130 °, which is lower than that of example 2.
Example 5
The method for preparing a nano-film using a hydrophobic material for low temperature plasma chemical vapor deposition includes the steps of:
(1) Preparing a hydrophobic material from an ethanol solution of a fluorine-containing acrylate monomer, propylene glycol methyl ether propionate, a polymerization inhibitor and a silane coupling agent; the polymerization inhibitor is benzoquinone, phenothiazine and piperidine nitrogen-oxygen free radical polymerization inhibitor, and the mass ratio is 30%:30%:40% of composite polymerization inhibitor; the silane coupling agent is selected from KH570, KH550 and KH560 according to the mass ratio of 1-50:1-50:1-50 of a mixture; the propylene glycol methyl ether propionate accounts for 5-10% of the mass ratio of the fluorine-containing acrylate monomer; the mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm; the mass ratio of the fluorine-containing acrylate monomer to the ethanol solution of the silane coupling agent is 70:20-90:5;
(2) Putting a workpiece to be processed into a reaction cavity, introducing pretreatment gas into the reaction cavity, starting a radio frequency power supply, and performing activation treatment on the surface of the workpiece in the reaction cavity by using plasma; the pretreatment gas is argon, the pressure of the reaction cavity is 0.08mbar, the flow of the argon is 100sccm, and the power of the continuous wave is 220W;
(3) Introducing the vaporized hydrophobic material into a reaction cavity, and depositing a nano film on the surface of the workpiece under pulse waves or continuous waves; dropping the vaporized hydrophobic material at the frequency of 3S/drop by controlling the flow, wherein the pressure of the reaction cavity is 0.06mbar, and the power of the pulse wave is 230W or the power of the continuous wave is 90W; the deposition time is 30min; introducing argon gas as a carrier gas while introducing the vaporized hydrophobic material, wherein the flow of the carrier gas is 100sccm;
(4) After the deposition of the nano film is finished, slowly breaking vacuum in the reaction cavity; the temperature and pressure of the deposited nano film are constantly maintained for 5min, and then the slow vacuum breaking is completed within 10 min;
(5) And after the vacuum breaking is finished, hermetically packaging the workpiece on which the nano film is deposited, and carrying out temperature and humidity adjustment treatment.
The static contact angle of the nano-film generated in this example was not significantly different from that of example 2. However, as the dripping frequency of the hydrophobic material is higher, the steam quantity of the hydrophobic material entering the reaction cavity once is higher, excessive reaction tends to occur, more yellow powdery solid particles are attached to the surface of the film, the appearance of the film sample changes color and turns yellow, and even more yellow powdery solid particles are attached to the inner wall of the cavity of the device.
Claims (8)
1. The method for preparing the nano film by the hydrophobic material for low-temperature plasma chemical vapor deposition is characterized by comprising the following steps of:
activation pretreatment: putting a workpiece to be processed into a reaction cavity, introducing pretreatment gas into the reaction cavity, starting a radio frequency power supply, and performing activation treatment on the surface of the workpiece in the reaction cavity by using plasma;
depositing a nano film: introducing the vaporized hydrophobic material into a reaction cavity, and depositing a nano film on the surface of the workpiece under pulse waves or continuous waves; the hydrophobic material comprises a fluorine-containing acrylate monomer, polyol ether ester and a polymerization inhibitor, wherein the mass ratio of the polyol ether ester to the fluorine-containing acrylate monomer is 5-10%, and the mass ratio of the polymerization inhibitor to the fluorine-containing acrylate monomer is 100-200ppm; the polyol ether ester comprises at least one of polyether polyol acetate, fatty alcohol polyether sulfonate, dodecanol ether phosphate, propylene glycol monomethyl ether propionate, isomeric tridecanol ether phosphate and fatty alcohol ether phosphate; the polymerization inhibitor is benzoquinone, phenothiazine and piperidine nitrogen-oxygen free radical polymerization inhibitor according to the mass ratio of 1-50%:1-50%:1-50% of composite polymerization inhibitor; dropping the vaporized hydrophobic material at the frequency of 5S/drop to 20S/drop of flow rate;
breaking vacuum: slowly breaking vacuum in the reaction cavity;
and (3) post-treatment: and sealing and packaging the workpiece on which the nano film is deposited, and carrying out temperature and humidity adjustment treatment.
2. The method according to claim 1, wherein the hydrophobic material further comprises an ethanol solution of a silane coupling agent, and the mass ratio of the fluorine-containing acrylate monomer to the ethanol solution of the silane coupling agent is 70:20-90:5.
3. the method according to claim 2, wherein the silane coupling agent is at least one of vinyl propyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethylsilane, 3-butenyl trimethylsilane, vinyl tributyrinoxime silane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, KH540, A171, KH570, KH550 and KH 560.
4. The method according to claim 2, wherein the silane coupling agent is KH570, KH550 and KH560 in a mass ratio of 1-50:1-50: 1-50.
5. The method of claim 1, wherein the hydrophobic material is obtained by uniformly mixing a fluorine-containing acrylate monomer, a polyol ether ester and a polymerization inhibitor.
6. The method as claimed in claim 2, wherein the hydrophobic material is obtained by uniformly mixing a fluorine-containing acrylate monomer, a polyol ether ester, a polymerization inhibitor and an ethanol solution of a silane coupling agent.
7. The method of claim 1, wherein in the step of depositing the nano-film, the plating power is 100-1000W; the deposition time is 10-120min; the thickness of the nano film is 50-1000nm.
8. The method according to claim 1, wherein in the step of the pre-activation treatment, the pre-treatment gas is argon gas, and a flow rate of the pre-treatment gas is 10 to 1000sccm; the power of the radio frequency power supply is 100-1000W; the pressure of the reaction cavity is 0.01-0.1mbar; the activation time is below 60min.
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